When aiming for an increased and more sustainable use of metals a thorough knowledge of the corrosion phenomenon as function of the local metal microstructure is of crucial importance. In this work, we summarize the information presented in our previous publications[1-3] and present an overview of the different local (electrochemical) techniques that have been proven to be effective in studying the relation between different microstructural variables and their different electrochemical behavior. Atomic force microscopy (AFM), scanning electrochemical microscopy (SECM), and electrochemical scanning tunneling microscopy (EC-STM) were used in combination with electron backscatter diffraction (EBSD). Consequently, correlations could be identified between the grain orientation and grain boundary characteristics, on the one hand, and the electrochemical behavior on the other hand. The grain orientation itself has an influence on the corrosion, and the orientation of the neighboring grains also seems to play a decisive role in the dissolution rate. With respect to intergranular corrosion, only coherent twin boundaries seem to be resistant.